JP5751497B2 - Resin composition and semiconductor device produced using resin composition - Google Patents

Description

The present invention relates to a resin composition and a semiconductor device manufactured using the resin composition.
This application claims priority on September 7, 2010 based on Japanese Patent Application No. 2010-199889 for which it applied to Japan, and uses the content here.

  In recent years, in the market trend aiming for miniaturization, weight reduction, and high functionality of electronic devices, higher integration and surface mounting of semiconductor devices are progressing year by year. For example, the number of pins / thinning is approaching the limit of the conventional surface mount semiconductor devices represented by Quad Flat Package (QFP) and Small Outline Package (SOP). In order to meet the demands for semiconductor devices, area mounted semiconductor devices such as lead frame-chip scale packages (LF-CSP) and ball grid arrays (BGA) have been newly developed as next-generation semiconductor devices. (Patent Document 1)

  The area mounting type semiconductor device is assembled in the following steps. First, a semiconductor element is mounted on one side of a metal or organic substrate by die attach paste or the like, and only the semiconductor element mounting surface, that is, one side of the substrate is molded and sealed with an epoxy resin composition or the like. Thereafter, a process (reflow process) of attaching bump electrodes (solder balls) to the surface of the substrate on which the semiconductor element is not mounted is performed. Further, an electronic device is manufactured by a process (secondary mounting process) for mounting the area mounting type semiconductor device on the mother board. Since area-mounted semiconductor devices are thinner than conventional packages with both sides sealed, warping due to the difference in thermal expansion coefficient between components tends to increase, and peeling and cracking during reflow are often a problem. Yes.

  Furthermore, as a part of environmental measures, removal and removal of lead components from solder used when a semiconductor device is mounted on a substrate is being promoted. Sn-Ag-Cu solder recommended by the Japan Electronics and Information Technology Industries Association (JEITA) (melting point: about 220 ° C.) is widely used as solder that does not contain lead components (hereinafter referred to as lead-free solder). Since the melting point is higher than that of Sn—Pb solder (melting point: about 200 ° C.), the problem of non-bonding due to the warping of the package when the semiconductor device is mounted has become more prominent. For this reason, the thermosetting adhesive composition used for bonding a semiconductor element to a circuit board or the like is increasingly required to suppress the warpage of the package with respect to an increase in the melting point temperature of the solder. Furthermore, since reflow treatment at a high temperature increases the stress inside the package, peeling and cracks are likely to occur in the semiconductor product during reflow.

  In addition, regarding the exterior plating of semiconductor products, there is an increasing number of cases where the lead frame plating is changed to nickel-palladium for the purpose of deleading. Here, regarding nickel-palladium plating, thin gold plating (gold flash) is performed for the purpose of improving the stability of the Pd layer on the surface, but because of the smoothness of nickel-palladium plating itself and the gold present on the surface, it is normal. Compared with a silver-plated copper frame or the like, the adhesive strength is reduced. The decrease in adhesive force causes peeling and cracks in the semiconductor product during the reflow process.

  In order to suppress the warpage of the package, a technique using a sealing resin having a low thermal expansion coefficient (Patent Document 2) has been proposed. Moreover, in order to suppress peeling, a technique (Patent Document 3) for improving the adhesion strength between the die pad and the sealing resin by making the die pad have a structure having good physical adhesion with the sealing resin. A technique (Patent Document 4) has been proposed such as increasing the glass transition point (Tg) and decreasing the elastic modulus at high temperature. In addition, a technique (Patent Document 5) that balances the low stress property and adhesiveness of an adhesive by using copolymerization of two different functional groups has been proposed. However, these methods alone cannot sufficiently solve the problems occurring in the semiconductor device.

  Thus, there is a demand for a material that is superior in adhesiveness and low stress in a high temperature environment as compared to conventionally used die attach pastes and can reduce the warpage of a semiconductor device.

JP 2003-109983 A JP 2000-216299 A Patent No. 3007632 JP 2000-72851 A WO2005-090510

  The present invention can impart excellent reliability to a semiconductor device with less warpage of the semiconductor device even in a high temperature environment during reflow, excellent interfacial adhesion, and no occurrence of defects such as peeling and cracking. A resin composition is provided.

（式中、Ｒ１は炭素原子数１以上の直鎖又は分枝アルキレン基を表し、Ｒ２は炭素原子数５以上の直鎖又は分枝アルキル基を表し、また、Ｒ１とＲ２の炭素原子数の和が１０以下である。）

（式中、Ｘ１は−Ｏ−、−ＣＯＯ−又は−ＯＣＯＯ−を表し、Ｒ３は炭素原子数１から５の直鎖又は分枝アルキレン基を表し、Ｒ４は炭素原子数３から６の直鎖又は分枝アルキレン基を表し、また、ｍは１以上５０以下の整数である。）
［２］更にアリルエステル基を有する化合物（Ｃ）を含む［１］に記載の樹脂組成物。
［３］前記アリルエステル基を有する化合物（Ｃ）が脂肪族環を有するものである［２］に記載の樹脂組成物。
［４］上記化合物Ｃが、一般式（３）の官能基を有する［３］に記載の樹脂組成物。

（式中、Ｒ^１は炭素原子数１〜１０の直鎖又は分枝アルキル基を表す。）
［５］更に充填剤を含む［１］乃至［４］のいずれか１つに記載の樹脂組成物。
［６］［１］乃至［５］のいずれか１つに記載の樹脂組成物を用いて作製した半導体装置。The above object is achieved by the present inventions [1] to [5] below.
[1] A resin composition comprising a maleimide derivative (A) represented by the general formula (1) and a bismaleimide compound (B) represented by the general formula (2).

(Wherein R1 represents a linear or branched alkylene group having 1 or more carbon atoms, R2 represents a linear or branched alkyl group having 5 or more carbon atoms, and R1 and R2 have the same number of carbon atoms) The sum is 10 or less.)

(Wherein X1 represents —O—, —COO— or —OCOO—, R3 represents a linear or branched alkylene group having 1 to 5 carbon atoms, and R4 represents a linear chain having 3 to 6 carbon atoms. Or a branched alkylene group, and m is an integer of 1 to 50.)
[2] The resin composition according to [1], further comprising a compound (C) having an allyl ester group.
[3] The resin composition according to [2], wherein the compound (C) having an allyl ester group has an aliphatic ring.
[4] The resin composition according to [3], wherein the compound C has a functional group represented by the general formula (3).

(In the formula, R ¹ represents a linear or branched alkyl group having 1 to 10 carbon atoms.)
[5] The resin composition according to any one of [1] to [4], further including a filler.
[6] A semiconductor device manufactured using the resin composition according to any one of [1] to [5].

  The resin composition of the present invention has excellent reliability in a semiconductor device in which the warpage of the semiconductor device is small even under a high temperature environment of 220 ° C. or more, excellent adhesion at the interface, and troubles such as peeling and cracking do not occur. It becomes possible to grant.

  The resin composition of the present invention comprises a maleimide derivative (A) represented by a predetermined chemical formula and a bismaleimide compound (B) represented by a predetermined chemical formula. Furthermore, the said effect can be aimed at by including the compound (C) which has an allyl ester group.

  Hereinafter, the present invention will be described in detail.

  In the present invention, a compound represented by the general formula (1) is used as the maleimide derivative (A). In the present specification, an acryl group including a functional group having a substituent at the α-position and / or β-position of the acryloyl group is used.

In general, a resin composition often uses a compound having one acrylic group as a reactive diluent. Of these, alkyl (meth) acrylates having a small number of carbon atoms such as methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate have high volatility. When such an alkyl (meth) acrylate is used for the resin composition, there is a problem that the bonding pad is contaminated by volatilization when the resin composition is cured, and the adhesive strength with the Au wire or the like is lowered. In addition, when it takes time to mount the adherend after applying the resin composition to the support, there is a problem that the spreadability of the resin composition is deteriorated and sufficient adhesive force cannot be obtained. . If an aliphatic acrylate having a relatively large number of carbon atoms such as lauryl (meth) acrylate or stearyl (meth) acrylate is used for the resin composition, the volatility is suppressed, but the dilution effect is not sufficient, and a high-viscosity resin composition is obtained. In some cases, deterioration of workability may be a problem. On the other hand, when a (meth) acrylate compound having a phenyl group is used for the resin composition, the volatility is suppressed, but there is a drawback that the dilution effect is not sufficient and the elastic modulus of the cured product is increased.
“(Meth) acrylate” means one or both of an acrylate having a hydrogen atom bonded to the α-position and a methacrylate having a methyl group bonded to the α-position.

  On the other hand, the maleimide derivative (A) represented by the general formula (1) used in the present invention can impart a good dilution effect and low volatility to the resin composition. Furthermore, in the resin composition containing the maleimide derivative (A), the curing temperature of the resin composition is shifted to a high temperature side due to the bulky maleimide group. Therefore, the warp at the time of reflow of a semiconductor device manufactured using this resin composition can be reduced.

  As for the structure of the maleimide derivative (A), R1 represents a linear or branched alkylene group having 1 or more carbon atoms, R2 represents a linear or branched alkyl group having 5 or more carbon atoms, and R1 and The sum of the carbon atoms of R2 is preferably 10 or less. With this structure, it is possible to give a good dilution effect and low stress, and to reduce the warpage of the semiconductor device at a high temperature. On the other hand, when the sum of the carbon atoms of R1 and R2 is less than 6, the dilution effect is improved, but the volatility becomes too high. Therefore, there is a problem that the bonding pad is contaminated by the volatilization when the resin composition is cured, and the adhesive strength with the Au wire or the like is lowered. In addition, when it takes time to mount the adherend after applying the resin composition to the support, there is a problem that the spreadability of the resin composition is deteriorated and sufficient adhesive force cannot be obtained. . When the sum of the number of carbon atoms of R1 and R2 is more than 6, or when R1 and R2 represent an aromatic ring, the volatility is suppressed, but the dilution effect is not sufficient, and the elastic modulus of the cured product is high. There is a drawback of becoming.

  As the maleimide derivative (A) represented by the general formula (1), for example, maleimide acetate n-pentyl, maleimide acetate n-hexyl, maleimide acetate n-heptyl, maleimide acetate n-octyl, maleimide acetate n-nonyl, maleimide acetate 1 -Methylbutyl, maleimidoacetic acid 2-methylbutyl, maleimidoacetic acid 2,2-dimethylpropyl, maleimidoacetate 2-ethylbutyl, maleimidoacetate 3,3-dimethylbutyl, maleimidoacetate 4-methylhexyl, maleimidoacetate 1-propylbutyl, maleimidoacetic acid 5 -Methylheptyl, 1-ethylhexyl maleimide acetate, 6-methyloctyl maleimide acetate, 1-ethylheptyl maleimide acetate, 3-iso-propylhexyl maleimide acetate, n-pentyl maleimide propionate, maleimide N-hexyl lopionate, n-heptyl maleimide propionate, n-octyl maleimide propionate, 1-ethylpropyl maleimide propionate, 3-methylbutyl maleimide propionate, 4-methylhexyl maleimide propionate, 3-iso- maleimide propionate Propylbutyl, 2-ethylbutyl maleimide propionate, 1-methylheptyl maleimide propionate, n-pentyl maleimide butyrate, n-hexyl maleimide butyrate, n-heptyl maleimide butyrate, 2,2-dimethylpropyl maleimide butyrate, 1-ethyl maleimide butyrate Propyl, 3-methylbutyl maleimide butyrate, 2-ethylbutyl maleimide butyrate, 3,3-dimethylbutyl maleimide butyrate, 2-methylpentyl maleimide butyrate, 1, , 2-trimethylpropyl, 1,3-dimethylbutyl maleimide butyrate, 4-methylhexyl maleimide butyrate, 1-methylhexyl maleimide butyrate, 1-propylbutyl maleimide butyrate, 3-methylhexyl maleimide butyrate, n-pentyl maleimide valerate, N-hexyl maleimide valerate, 3-methylbutyl maleimide valerate, 2,2-dimethylpropyl maleimide valerate, 1-ethylpropyl maleimide valerate, 2-methylpentyl maleimide valerate, 3-methylpentyl maleimide valerate, maleimide yoshi 3,3-dimethylbutyl herbate, 1,2-dimethylbutyl maleimide valerate, 1-ethylbutyl maleimide valerate, 1-ethyl-1-methylpropyl maleimide valerate, n-pentyl maleimide caproate, 2-methalemate caproate 2-me Examples include, but are not limited to, butyl butyl, 2,2-dimethylpropyl maleimide caproate, 3-methylbutyl maleimide caproate, 1,2-dimethylpropyl maleimide caproate, 1-ethylpropyl maleimide caproate. . These may be used alone or in combination of two or more.

  Here, the maleimide derivative (A) is preferably contained in an amount of 1 to 10% by weight, more preferably 1 to 6% by weight, based on the entire resin composition. If it is the said range, the favorable dilution effect and low volatility can be provided to a resin composition, and also the curvature at the time of the high temperature of a semiconductor device can be decreased by using this resin composition.

  As the bismaleimide compound (B) used in the present invention, a compound represented by the general formula (2) is used. The bismaleimide compound (B) is a compound that contains two maleimide groups in one molecule, and forms a three-dimensional network structure by the reaction of the maleimide groups by heating, and is a cured resin.

  The bismaleimide compound (B) contains a maleimide group or a derivative thereof as a functional group, and when used together with a thermal radical polymerization initiator described later, it exhibits good reactivity under heating and has an imide ring. This is because, due to the polarity of the metal, it exhibits good adhesion even to a hard-to-adhere metal surface such as nickel-palladium plating.

  From the viewpoint of curability, bismaleimide having two maleimide rings in one molecule is preferable. The two maleimide rings and an alkylene group composed of an aliphatic hydrocarbon may be bonded via an ether bond or an ester bond. Also, it has two functional groups in one molecule, but this is not sufficient for the expected adhesion improvement effect in the case of one function, and the molecular weight increases in the case of three or more functions, so the viscosity increases. This is because the viscosity of the resin composition is increased. Here, as bismaleimide compounds, those using aromatic amines as raw materials are well known, but generally, aromatic maleimides have strong crystallinity and it is difficult to obtain liquid compounds at room temperature. Further, such a maleimide compound is soluble in a high-boiling polar solvent such as dimethylformamide or N-methylpyrrolidone. However, when such a solvent is used, a void is formed during heat curing of the resin composition. Is generated and the thermal conductivity is deteriorated. Since the bismaleimide compound (B) is in a liquid state at room temperature, it is not necessary to use a solvent and can be preferably used.

  R3 in the general formula (2) is a hydrocarbon group having 1 to 5 carbon atoms. When the number of carbon atoms is 6 or more, the crystallinity becomes high and cannot be used. R3 preferably has 1 or 5 carbon atoms, and particularly preferably has 1 carbon atoms.

  R4 in the general formula (2) is a hydrocarbon group having 3 to 6 carbon atoms. If the number of carbon atoms is less than this range, the water absorption characteristics are deteriorated, and the characteristics such as adhesive strength are deteriorated under severe water absorption conditions such as a pressure cooker test. When the number of carbon atoms is larger than this range, the resin composition becomes too hydrophobic, resulting in poor adhesion to a metal surface such as copper, which is easily oxidized, and high crystallinity. A more preferable carbon number is 3 or 4.

  X1 contains an -O-, -COO- or -OCOO- group, which is necessary for exhibiting flexible cured product properties and is liquid as a raw material or dissolved in other components. This is because it is also necessary to improve the performance. Among these, the case where X1 is -O- is preferable. Further, if the number of repetitions m is more than 50, the viscosity becomes too high, which is not preferable in practice. Here, as long as the repeating unit satisfies the above conditions, a copolymer of two or more kinds or other components can be used.

  Such a compound is a compound having an amide group and a carboxy group and having a hydrocarbon group having 1 to 5 carbon atoms between the amide group and the carboxy group (glycine, alanine, aminocaproic acid, etc.), and maleic anhydride It can be obtained by synthesizing a maleimidated amino acid by reacting with an acid or a derivative thereof, and reacting the obtained compound with polyalkylene oxide diol, polyalkylene ester diol or the like.

  As the compound (C) having an allyl ester group, generally known compounds can be used. Examples thereof include, but are not limited to, diallyl phthalate, diallyl terephthalate, diallyl isophthalate, triallyl trimellitate, diallyl malate, allyl methacrylate, and allyl acetoacetate.

  The compound (C) has at least one allyl ester group in one molecule, but preferably has two or three from the viewpoint of curability. As the number of functional groups in one molecule increases, the molecular weight increases accordingly, so that the viscosity generally tends to increase. For this reason, when considering the balance between curability and workability, the most preferable number of functional groups is two in one molecule.

  The number average molecular weight of the compound (C) is not particularly limited, but is preferably 500 or more and 10,000 or less, and particularly preferably 500 or more and 8,000 or less. When the number average molecular weight is within the above range, curing shrinkage can be particularly reduced, and deterioration of adhesion can be prevented.

  Examples of the compound (C) having the number average molecular weight as described above include terephthalic acid, isophthalic acid, phthalic acid, 5-norbornene-endo-2,3-dicarboxylic acid, 1,4-dicyclodicarboxylic acid, and adipic acid. And an allyl ester-based compound in which allyl alcohol is added by esterification to the terminal of a polyester synthesized from a dicarboxylic acid such as dicarboxylic acid or a methyl ester derivative thereof and an alkylene diol having 2 to 8 carbon atoms.

  It is preferable that a compound (C) does not have an aromatic ring. This is because the aromatic ring has a rigid structure, and the presence of the aromatic ring increases the rigidity of the cured product so that the cured product becomes brittle, and as a result, cracks are likely to occur in the semiconductor device. In general, when an aromatic ring is included, since the resin has high crystallinity, it is difficult to obtain a liquid at room temperature, and workability at the time of dispensing application deteriorates. From the viewpoint of solving such a problem, it is more preferable to have a functional group represented by the general formula (3). With the structure having an aliphatic ring, the workability is good, and the resin composition is suppressed in brittleness even in a high-temperature environment during reflow, and the occurrence of cracks and the like in the semiconductor device can be suppressed.

  Moreover, in order to adjust various properties of the resin composition of the present invention, the following compound (D) having a functional group capable of radical polymerization can be used as long as the effects of the present invention are not impaired. For example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxy Butyl (meth) acrylate, glycerin mono (meth) acrylate, glycerin di (meth) acrylate, trimethylolpropane mono (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol mono (meth) acrylate, pentaerythritol di ( (Meth) acrylates having hydroxyl groups such as (meth) acrylate, pentaerythritol tri (meth) acrylate, neopentyl glycol mono (meth) acrylate, and these hydroxyl groups Such as a (meth) having an acrylate and a dicarboxylic acid or a carboxy group obtained by reacting the derivative (meth) acrylate. Examples of dicarboxylic acids that can be used here include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, and tetrahydrophthalic acid. , Hexahydrophthalic acid and derivatives thereof.

  In addition to the above, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tertiary butyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, Tridecyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, other alkyl (meth) acrylates, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, glycidyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, Zinc mono (meth) acrylate, zinc di (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, neopentyl glycol (meta Acrylate, trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 2,2,3,3,4,4-hexafluorobutyl (meth) acrylate, perfluorooctyl ( (Meth) acrylate, perfluorooctylethyl (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) ) Acrylate, 1,9-nonanediol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, methoxyethyl (Meth) acrylate, Toxiethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, polyethylene glycol di (meth) acrylate, N, N′-methylenebis (meth) acrylamide, N, N′-ethylenebis (meth) acrylamide, 1,2-di ( (Meth) acrylamide ethylene glycol, di (meth) acryloyloxymethyl tricyclodecane, N- (meth) acryloyloxyethyl maleimide, N- (meth) acryloyloxyethyl hexahydrophthalimide, N- (meth) acryloyloxy It is also possible to use ethylphthalimide, n-vinyl-2-pyrrolidone, styrene derivatives, α-methylstyrene derivatives and the like.

  The resin composition of the present invention preferably further contains a polymerization initiator from the viewpoint of controlling the initiation reaction of radical polymerization. A thermal radical polymerization initiator is preferably used as the polymerization initiator. Although it is not particularly limited as long as it is normally used as a thermal radical polymerization initiator, it is desirable that a rapid heating test (decomposition start temperature when a sample is placed on an electric heating plate and heated at 4 ° C./min. In which the decomposition temperature is 40 to 140 ° C. If the decomposition temperature is less than 40 ° C., the preservability of the resin composition at normal temperature deteriorates, and if it exceeds 140 ° C., the curing time becomes extremely long, which is not preferable.

  Specific examples of the thermal radical polymerization initiator satisfying this include methyl ethyl ketone peroxide, methylcyclohexanone peroxide, methyl acetoacetate peroxide, acetylacetone peroxide, 1,1-bis (t-butylperoxy) 3, 3, 5 -Trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) ) Cyclohexane, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane, 1,1-bis (t-butylperoxy) cyclododecane, n-butyl 4,4-bis (t- Butyl peroxy) valerate, 2,2-bis (t-butylperoxy) Tan, 1,1-bis (t-butylperoxy) -2-methylcyclohexane, t-butyl hydroperoxide, P-menthane hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, t -Hexyl hydroperoxide, dicumyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, α, α'-bis (t-butylperoxy) diisopropylbenzene, t-butyl Cumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3, isobutyryl peroxide, 3,5,5-trimethylhexanoyl peroxide , Octanoyl peroxide, lauroyl peroxide, cinnamic acid peroxide m-toluoyl peroxide, benzoyl peroxide, diisopropyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, di-3-methoxybutyl peroxydicarbonate, di-2-ethylhexyl peroxide Carbonate, di-sec-butylperoxydicarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, di (4-t-butylcyclohexyl) peroxydicarbonate, α, α′-bis (neo) Decanoylperoxy) diisopropylbenzene, cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, t-Hexylpao Cineodecanoate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, t-butylperoxypivalate, 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) ) Hexane, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethyl Hexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, t-butylperoxymaleic acid, t-butylperoxylaurate, t-butylperoxy-3 , 5,5-trimethylhexanoate, t-butylperoxyisopropyl monocarbonate, t Butylperoxy-2-ethylhexyl monocarbonate, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, t-butylperoxyacetate, t-hexylperoxybenzoate, t-butylperoxy-m- Toluoyl benzoate, t-butylperoxybenzoate, bis (t-butylperoxy) isophthalate, t-butylperoxyallyl monocarbonate, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) Examples thereof include benzophenone, but these can be used alone or in combination of two or more in order to control curability.

  In the present invention, it is also possible to add a filler. Thereby, adjustment of viscosity and thixotropy, toughening of the resin composition, and the like are possible, and handling such as application to a support or a semiconductor element becomes easy.

  Metal powder such as silver, platinum, gold, nickel, iron, tin, copper, palladium, etc. for providing conductivity to the filler used in the present invention; metal coat powder having a conductive layer on the surface of silver coat powder, etc. A generally known conductive filler such as carbon powder such as carbon black and graphite can be used. Among these, silver is preferably used from the viewpoint of conductivity. Moreover, in order to adjust the various characteristics of the resin composition of this invention, it is also possible to use a filler in the range which does not impair the effect of a conductive filler. Examples of the filler include ceramic particles such as silica and alumina, or thermosetting resin and thermoplastic resin particles.

  In order to impart insulating properties, for example, ceramic particles such as silica and alumina, or thermosetting resin or thermoplastic resin particles can be used.

  The shape of particles generally used as a filler includes various shapes such as a scale shape, a spherical shape, a resin shape, and a powder shape, but the shape is not particularly limited in the present invention.

  In the case of silver, for example, the content of the filler is preferably 60% by weight or more and 90% by weight or less, and particularly 70% by weight or more and 85% by weight of the entire thermosetting adhesive composition according to the present invention. The following is preferable. Moreover, it is preferable that content of a filler is 20 volume% or more and 50 volume% or less of the whole thermosetting adhesive composition which concerns on this invention. By setting the content within the above range, viscosity and thixotropy can be made suitable, and workability can be improved.

  The average particle diameter of the filler is preferably 1 μm or more and 10 μm or less, and particularly preferably 2 μm or more and 7 μm or less. By setting the average particle diameter to be equal to or larger than the lower limit, the viscosity of the adhesive composition can be made suitable. Moreover, the problem at the time of shaping | molding of a nozzle etc. can be reduced by setting it as the said upper limit or less. In addition, the said average particle diameter can be measured using the particle size distribution measuring apparatus which used the laser diffraction / scattering method, for example.

  In the present invention, a coupling agent can be used from the viewpoint of improving adhesive strength. Commonly used silane coupling agents and titanium coupling agents can be used. In particular, a silane coupling agent having an S—S bond also produces a bond with the surface of the silver powder when silver powder is used as an inorganic filler, so that not only the adhesion to the adherend surface but also the cohesion of the cured product is improved. To do. Therefore, a silane coupling agent having an S—S bond can be preferably used. Examples of the silane coupling agent having an S—S bond include bis (trimethoxysilylpropyl) monosulfide, bis (triethoxysilylpropyl) monosulfide, bis (tributoxysilylpropyl) monosulfide, and bis (dimethoxymethylsilylpropyl). Monosulfide, bis (diethoxymethylsilylpropyl) monosulfide, bis (dibutoxymethylsilylpropyl) monosulfide, bis (trimethoxysilylpropyl) disulfide, bis (triethoxysilylpropyl) disulfide, bis (tributoxysilylpropyl) Disulfide, bis (dimethoxymethylsilylpropyl) disulfide, bis (diethoxymethylsilylpropyl) disulfide, bis (dibutoxymethylsilylpropyl) disulfide, bis ( Rimethoxysilylpropyl) trisulfide, bis (triethoxysilylpropyl) trisulfide, bis (tributoxysilylpropyl) trisulfide, bis (dimethoxymethylsilylpropyl) trisulfide, bis (diethoxymethylsilylpropyl) trisulfide, bis (Dibutoxymethylsilylpropyl) trisulfide, bis (trimethoxysilylpropyl) tetrasulfide, bis (triethoxysilylpropyl) tetrasulfide, bis (tributoxysilylpropyl) tetrasulfide, bis (dimethoxymethylsilylpropyl) tetrasulfide, Bis (diethoxymethylsilylpropyl) tetrasulfide, bis (dibutoxymethylsilylpropyl) tetrasulfide, bis (trimethoxysilylpropyl) polysulfide Sulfide, bis (triethoxysilylpropyl) polysulfide, bis (tributoxysilylpropyl) polysulfide, bis (dimethoxymethylsilylpropyl) polysulfide, bis (diethoxymethylsilylpropyl) polysulfide, bis (dibutoxymethylsilylpropyl) polysulfide etc. These silane coupling agents having an S—S bond may be used alone or in combination of two or more.

  Moreover, the combined use with the silane coupling agent which has a S-S bond, and other than the silane coupling agent which has a S-S bond is also preferable. Examples of the silane coupling agent other than the silane coupling agent having an S—S bond that are preferably used include allyltriethoxysilane, allyltrimethoxysilane, diethoxymethylvinylsilane, triethoxyvinylsilane, vinyltrimethoxysilane, vinyltris (2- Methoxyethoxy) silane, 3-glycidyloxypropyl (dimethoxy) methylsilane, 3-glycidyloxypropyltrimethoxysilane, diethoxy (3-glycidyloxypropyl) methylsilane, 3- (2-aminoethylamino) propyldimethoxymethylsilane, 3- (2-aminoethylamino) propyltriethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, 3-aminopropyldiethoxymethylsilane, 3-aminopropyltriethoxysilane 3-aminopropyltrimethoxysilane, (3-mercaptopropyl) triethoxysilane, (3-mercaptopropyl) trimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3- (isocyanate) Triethoxysilyl) propyl, 3- (trimethoxysilyl) propyl acrylate, 3- (trimethoxysilyl) propyl methacrylate, triethoxy-1H, 1H, 2H, 2H-tridecafluoro-n-octylsilane, 2-cyanoethyl Triethoxysilane, diacetoxydimethylsilane, diethoxydimethylsilane, dimethoxydimethylsilane, dimethoxydiphenylsilane, dimethoxymethylphenylsilane, hexyltrimethoxysilane, n-dodecyltriethoxysilane, n-octyltriethoxysilane , Octadecyltriethoxysilane, octadecyltrimethoxysilane, pentyltriethoxysilane, triacetoxymethylsilane, triethoxyethylsilane, triethoxymethylsilane, trimethoxy (methyl) silane, trimethoxy (propyl) silane, trimethoxyphenylsilane, etc. It is done. Furthermore, a titanium coupling agent and an aluminum coupling agent can be used as necessary.

  In the resin composition of the present invention, additives such as a low stress agent, an antifoaming agent, a surfactant, various polymerization inhibitors and antioxidants can be used as necessary.

  The resin composition of the present invention can be produced, for example, by premixing each component, kneading using three rolls, and degassing under vacuum.

  As a method of manufacturing a semiconductor device using the resin composition of the present invention, a known method can be used. For example, using a commercially available die bonder, the resin composition is dispensed on a predetermined portion of the lead frame, and then the chip is mounted and heat-cured. Then, a semiconductor device is manufactured by wire bonding and transfer molding using an epoxy resin. Alternatively, the resin composition is dispensed on the back side of a chip such as flip chip BGA (Ball Grid Array) sealed with an underfill material after flip chip bonding, and heat curing components such as heat spreaders and lids are mounted and cured. Is also possible.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example and a comparative example, this invention is not limited to this. In Examples 1-5 and Comparative Examples 1-6, the following raw materials were blended in parts by weight shown in Table 1, and then kneaded and degassed using three rolls to obtain resin compositions.

(Compound (A))
Synthesis examples of maleimide derivatives (A) (A1 to A6) are shown below. The synthesis method is not limited to the following method, and various known methods can be used.

(Synthesis Example 1)
(Compound A1: Synthesis of n-pentyl maleimide acetate)
A separable flask equipped with a Dean-Stark trap was charged with maleimide acetic acid (reagent) 31.0 (0.2 mol), p-toluenesulfonic acid (reagent) 5.2 g (0.03 mol), and toluene (reagent) 300 ml. Thereafter, 17.6 g (0.2 mol) of n-pentanol (reagent) was added dropwise, and the mixture was allowed to react with stirring at 80 ° C. for 1 hour under reduced pressure. After the dropwise addition, the reaction was further stirred for 4 hours. Meanwhile, the produced water was removed by a Dean Stark trap. After the reaction, 300 ml of toluene was added, and the resulting organic phase was collected after washing with 100 ml of ion exchange water three times. The toluene was distilled off using an evaporator and a vacuum dryer, and 43.5 g of maleimidoacetic acid n-pentyl was added. Obtained. (Yield about 91%. It was confirmed by GPC measurement that maleimide acetic acid and n-pentanol did not remain. The presence of maleimidoacetic acid n-pentyl was confirmed by ¹ H-NMR measurement using DMSO-d6. (Hereinafter referred to as Compound A1)
In Compound A1, R1 is an alkylene group having 1 carbon atom, R2 is a linear alkyl group having 5 carbon atoms, and the sum of R1 and R2 is 6.

(Physical properties of compound A1)
¹ H-NMR (400 MHz, DMSO-d6): 6.9 ppm (2H, —CH═CH—), 4.0 ppm (2H, —CH ₂ —COO—), 3.8 ppm (2H, —O—CH ₂₎ −)

(Synthesis Example 2)
(Compound A2: Synthesis of 2-ethylbutyl maleimide acetate)
In Synthesis Example 2, 47.3 g of 2-ethylbutyl maleimide acetate was obtained in the same manner as in Synthesis Example 1 except that 20.0 g of 2-ethylbutanol (reagent) was used instead of 17.6 g of n-pentanol. . (Confirming the presence of maleimide acetic acid 2-ethylbutyl by measuring the yield of about maleimide acetate at 88% .GPC measurement, ¹ H-NMR of 2-ethyl-butanol was used .DMSO-d6 confirming that no remaining Hereinafter referred to as Compound A2.)
In Compound A2, R1 is an alkylene group having 1 carbon atom, R2 is a branched alkyl group having 6 carbon atoms, and the sum of R1 and R2 is 7.

(Physical property value of compound A2)
¹ H-NMR (400 MHz, DMSO-d6): 6.9 ppm (2H, —CH═CH—), 4.0 ppm (2H, —CH ₂ —COO—), 3.8 ppm (2H, —O—CH ₂₎ −)

(Synthesis Example 3)
(Compound A3: Synthesis of n-pentyl maleimide caproate)
In Synthesis Example 1, 45.2 g of maleimidocaproic acid n-pentyl was obtained in the same manner as in Synthesis Example 1 except that 38.6 g of maleimidocaproic acid (reagent) was used instead of 31.0 g of maleimidoacetic acid. (Yield: about 86%. It was confirmed by GPC measurement that maleimide acetic acid and n-pentanol did not remain. The presence of maleimidocaproate n-pentyl was confirmed by ¹ H-NMR measurement using DMSO-d6. (Hereinafter referred to as Compound A3)
In Compound A3, R1 is a linear alkylene group having 5 carbon atoms, R2 is a linear alkyl group having 5 carbon atoms, and the sum of R1 and R2 is 10.

(Physical properties of compound A3)
¹ H-NMR (400 MHz, DMSO-d6): 6.9 ppm (2H, —CH═CH—), 2.3 ppm (2H, —CH ₂ —COO—), 3.7 ppm (2H, —O—CH ₂₎ −)

(Synthesis Example 4)
(Compound A4: Synthesis of ethyl maleimide ethyl acetate)
In a separable flask, 279 g (2 mol) of glycine ethyl hydrochloride (reagent) was mixed with 800 ml of acetic anhydride (reagent), and then 196 g (2 mol) of maleic anhydride (reagent) was dissolved in 600 ml of acetic anhydride while stirring at room temperature. What was made to drop was dripped over 3 hours. After the dropwise addition, the resulting precipitate was further stirred for 1 hour, collected by suction filtration, washed with ion-exchanged water, and dried. 382 g of the obtained product, 404 g (4 mol) of triethylamine (reagent) and 1200 ml of toluene were charged into a separable flask equipped with a Dean-Stark trap, and reacted at 120 ° C. with stirring for 2 hours. Meanwhile, the produced water was removed by a Dean Stark trap. After the reaction, 300 ml of toluene was added, and after washing with ion-exchanged water three times, the obtained organic phase was collected, and toluene was distilled off using an evaporator and a vacuum dryer to obtain 165 g of maleimidoethyl acetate. (Yield: about 38%. Production of ethyl maleimidoacetate was confirmed by GPC measurement. The presence of maleimidoethyl acetate was confirmed by ¹ H-NMR measurement using DMSO-d6, hereinafter referred to as compound A4.)
In Compound A4, R1 is an alkylene group having 1 carbon atom, R2 is a linear alkyl group having 2 carbon atoms, and the sum of R1 and R2 is 3.

(Physical properties of compound A4)
¹ H-NMR (400 MHz, DMSO-d6): 6.9 ppm (2H, —CH═CH—), 4.0 ppm (2H, —CH ₂ —COO—), 3.8 ppm (2H, —O—CH ₂₎ −)

(Synthesis Example 5)
(Compound A5: Synthesis of tert-butyl maleimide acetate)
In Synthesis Example 1, 35.0 g of tert-butyl maleimide acetate was obtained in the same manner as in Synthesis Example 1 except that 3.7 g of tert-butanol (reagent) was used instead of 17.6 g of n-pentanol. (Confirmed the presence of maleimide acetate tert- butyl by ¹ H-NMR measurement of maleimide acetic acid at a yield of about 83% .GPC measurement and tert- butanol with .DMSO-d6 confirming that no remaining Hereinafter referred to as Compound A5.)
In Compound A5, R1 is an alkylene group having 1 carbon atom, R2 is a branched alkyl group having 4 carbon atoms, and the sum of R1 and R2 is 5.

(Physical properties of compound A5)
¹ H-NMR (400 MHz, DMSO-d6): 6.9 ppm (2H, —CH═CH—), 4.1 ppm (2H, —CH ₂ —COO—), 1.5 ppm (9H, —O—C ( CH ₃ ) ₃ )

(Synthesis Example 6)
(Compound A6: Synthesis of 2-ethylbutyl maleimide benzoate)
In Synthesis Example 3, 50.4 g of 2-ethylbutyl maleimide benzoate was obtained in the same manner as in Synthesis Example 1 except that 43.4 g of maleimide benzoic acid was used instead of 31.0 g of maleimide acetic acid. (Yield: about 80%. It was confirmed by GPC measurement that maleimide benzoic acid and 2-ethylbutanol did not remain. Presence of 2-ethylbutyl maleimide benzoate by ¹ H-NMR measurement using DMSO-d6. (Hereinafter referred to as Compound A6)
In Compound A6, R1 is a phenylene group having an aromatic ring having 6 carbon atoms, R2 is a branched alkyl group having 6 carbon atoms, and the sum of the number of carbon atoms of R1 and R2 is 12. is there.

(Physical properties of compound A6)
¹ H-NMR (400 MHz, DMSO-d6): 7.5 to 8.0 ppm (4H, —C ₆ H ₄ —), 7.0 ppm (2H, —CH═CH—), 3.8 ppm (2H, − O—CH ₂ —)

(Bismaleimide compound)
Compound B: Polyalkylenemaleimide acetate obtained by reaction of polytetramethylene glycol and maleimidated acetic acid (DIC Corporation, LumiCure MIA-200, molecular weight 580, hereinafter referred to as Compound B)

(Compound having an allyl ester group)
Compound C: diallyl ester compound obtained by reaction of diallyl ester of cyclohexanedicarboxylic acid and propylene glycol (manufactured by Showa Denko KK, DA101, molecular weight 1000, hereinafter referred to as compound C)

(Compound having a functional group capable of radical polymerization)
Compound D: Polyethylene glycol di (meth) acrylate (manufactured by Kyoeisha Chemical Co., Ltd., light ester 4EG, hereinafter referred to as compound D)

(Reactive diluent)
Reactive diluent: 2-methacryloyloxyethyl succinic acid (manufactured by Kyoeisha Chemical Co., Ltd., light ester HOMS, hereinafter simply referred to as reactive diluent)

(Initiator)
Radical polymerization initiator: 1,1-di (tert-butylperoxy) cyclohexane (manufactured by NOF Corporation, Perhexa CS, hereinafter simply referred to as initiator)

(Filler)
Filler: Flaky silver powder having an average particle diameter of 3 μm and a maximum particle diameter of 20 μm (in all Examples and Comparative Examples, the filler content was set to 22% by volume)

(Additive)
In addition to the above compounds and fillers, the following additives were used.
Coupling agent 1: γ-glycidylpropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403E, hereinafter referred to as coupling agent 1)
Coupling agent 2: bis (trimethoxysilylpropyl) tetrasulfide (Daiso Co., Ltd., Cabras 4, hereinafter referred to as coupling agent 2)

(Evaluation test)
The following evaluation tests were conducted on the resin compositions and semiconductor devices of Examples and Comparative Examples obtained above. The evaluation results are shown in Table 1.

(Curve evaluation 1)
(Manufacture of semiconductor devices)
Nickel-palladium plated copper frame (die pad size: 8 x 8 mm, thickness 220 μm, 4 rows of die pads per panel x 4) with Kapton tape attached to the back surface to prevent bleeding of the sealing resin as a support The support and the semiconductor element (5 × 5 mm, thickness 350 μm) having the SiN layer on the surface are bonded with the resin compositions of the above-described examples and comparative examples, and the oven is heated at 175 ° C. for 30 minutes. Cured inside and bonded. Next, using an epoxy resin composition for semiconductor encapsulation (EME-G620, manufactured by Sumitomo Bakelite Co., Ltd.), one panel 50 mm × 50 mm and one panel including the lead frame are sealed to 750 μm, and 175 ° C. Post mold cure was performed for 4 hours, and then separated into pieces with a dicing saw or the like to obtain a test semiconductor device (84LQFN, size 10 × 10 mm, sealing resin thickness 750 μm). The warp of the test semiconductor device after heating at 260 ° C. was defined as the warp amount.

(Warpage measurement method)
The warpage amount defined as described above was measured and calculated by the following method.
Warpage amount: average height HE of the four corners of the above-mentioned test semiconductor device end and the height of the central portion of the test semiconductor device using a temperature variable laser three-dimensional measuring machine (manufactured by Hitachi Engineering & Service, LSI-150) HC was measured, and the difference between the HE and the HC, that is, the numerical value obtained by the following equation 1 was used as the warpage amount.
Formula 1: Warpage amount = HE-HC

(Adhesion strength)
Using the resin compositions of Examples and Comparative Examples described above, a 5 × 5 mm silicon chip (thickness of 525 μm) was mounted on a support nickel-palladium plated copper frame, and 175 ° C. for 15 minutes (25 After curing at a curing temperature profile of 5 ° C./min from a temperature rising rate of 175 ° C. to 175 ° C., the hot die shear strength in a 260 ° C. environment was measured. The obtained strength was defined as adhesion strength (unit: N / chip). Usually, if adhesion strength of 30N or more is obtained, it will not be peeled off at the time of wire bonding or sealing.

(Workability)
Using an E-type viscometer (3 ° cone), the values at 25 ° C. and 2.5 rpm were measured immediately after the production of the resin compositions of Examples and Comparative Examples. The case where the viscosity was 15 to 30 Pa · s was regarded as acceptable. The unit of viscosity is Pa · s.

(Wire adhesion strength)
Using the resin compositions of Examples and Comparative Examples described above, a silicon chip having an electrode with a composition of Al-1% Si-0.5% Cu was bonded to a lead frame made of 42 alloy plated with Ag, Au wire was bonded. A tensile test was conducted by hooking the bonded wires. At that time, when the adhesion strength of the wire is sufficient, it breaks at the wire portion, but when the adhesion strength is insufficient, the wire and the bonding pad are peeled off. Each code | symbol in Table 1 is as follows.
○: Peeling at the joint is less than 10% of the whole (pass).
X: Peeling at the joint is 10% or more of the whole (defect).

(Reflow resistance)
Nickel-palladium plated copper frame (die pad size: 8 x 8 mm, thickness 220 μm, 4 rows of die pads per panel x 4) with Kapton tape attached to the back surface to prevent bleeding of the sealing resin as a support The support and the semiconductor element (5 × 5 mm, thickness 350 μm) having the SiN layer on the surface are bonded with the resin compositions of the above-described examples and comparative examples, and the oven is heated at 175 ° C. for 30 minutes. Cured inside and bonded. Next, using an epoxy resin composition for semiconductor encapsulation (EME-G620, manufactured by Sumitomo Bakelite Co., Ltd.), one panel 50 mm × 50 mm and one panel including the lead frame are sealed to 750 μm, and 175 ° C. Post mold cure was performed for 4 hours, and then separated into pieces with a dicing saw or the like to obtain a test semiconductor device (84LQFN, size 10 × 10 mm, sealing resin thickness 750 μm). This test semiconductor device was subjected to moisture absorption treatment at 60 ° C. and 60% relative humidity for 120 hours, followed by IR reflow treatment (260 ° C., 10 seconds, 3 times reflow), and the treated package was subjected to ultrasonic deep scratches. The ratio of the peeled area was measured with an apparatus (transmission type), and the case where it was less than 10% was regarded as acceptable.

The resin composition of the present invention provides excellent reliability to a semiconductor device in which the warpage of the semiconductor device is small even in a high temperature environment at the time of reflow, the interfacial adhesion is excellent, and defects such as peeling and cracking do not occur. can do.

Claims (6)

A resin composition comprising a maleimide derivative (A) represented by the general formula (1) and a bismaleimide compound (B) represented by the general formula (2).

(Wherein R1 represents a linear or branched alkylene group having 1 or more carbon atoms, R2 represents a linear or branched alkyl group having 5 or more carbon atoms, and R1 and R2 have the same number of carbon atoms) The sum is 10 or less.)

(In the formula, X 1 represents —O—, —COO— or —OCOO—, R 3 represents a linear or branched alkylene group having 1 to 5 carbon atoms, and R 4 represents a linear chain having 3 to 6 carbon atoms. Or a branched alkylene group, and m is an integer of 1 to 50.)   Furthermore, the resin composition of Claim 1 containing the compound (C) which has an allyl ester group.   The resin composition according to claim 2, wherein the compound (C) having an allyl ester group has an aliphatic ring. The resin composition according to claim 3, wherein the compound C has a functional group represented by the general formula (3).

(In the formula, R ¹ represents a linear or branched alkyl group having 1 to 10 carbon atoms.)   The resin composition according to claim 1, further comprising a filler.   A semiconductor device produced using the resin composition according to claim 1.